U.S. patent application number 13/956884 was filed with the patent office on 2015-02-05 for organic-inorganic hybrid material film and method for manufacturing the same.
This patent application is currently assigned to ITEQ CORPORATION. The applicant listed for this patent is ITEQ CORPORATION. Invention is credited to Ming-Hung HUANG, Chao-Hui KUO, Po-Hsun LEE, Shun-Cheng WANG.
Application Number | 20150038039 13/956884 |
Document ID | / |
Family ID | 52428084 |
Filed Date | 2015-02-05 |
United States Patent
Application |
20150038039 |
Kind Code |
A1 |
KUO; Chao-Hui ; et
al. |
February 5, 2015 |
ORGANIC-INORGANIC HYBRID MATERIAL FILM AND METHOD FOR MANUFACTURING
THE SAME
Abstract
The invention provides a method for manufacturing an
organic-inorganic hybrid material film. The method mainly comprises
hybridization of polymaleic anhydride-polyimide and silica by
sol-gel route and by using a silane coupling agent to produce a
structure of polymaleic anhydride-polyimide having silane, then
casting and curing to form a material film. Also, the invention
provides a polymaleic anhydride-polyimide-silica organic-inorganic
hybrid material film.
Inventors: |
KUO; Chao-Hui; (Taoyuan
County, TW) ; HUANG; Ming-Hung; (Taoyuan County,
TW) ; LEE; Po-Hsun; (Taoyuan County, TW) ;
WANG; Shun-Cheng; (Taoyuan County, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ITEQ CORPORATION |
Taoyuan County |
|
TW |
|
|
Assignee: |
ITEQ CORPORATION
Taoyuan County
TW
|
Family ID: |
52428084 |
Appl. No.: |
13/956884 |
Filed: |
August 1, 2013 |
Current U.S.
Class: |
442/180 ;
427/387; 428/221; 524/549 |
Current CPC
Class: |
H05K 1/0346 20130101;
H05K 1/0366 20130101; H05K 1/0353 20130101; H05K 2201/0154
20130101; B32B 15/14 20130101; B32B 2260/021 20130101; Y10T
428/249921 20150401; H05K 2203/1168 20130101; B32B 2262/101
20130101; H05K 2201/0162 20130101; B32B 15/20 20130101; B32B
2307/206 20130101; H05K 1/0306 20130101; Y10T 442/2992
20150401 |
Class at
Publication: |
442/180 ;
524/549; 427/387; 428/221 |
International
Class: |
C09D 151/00 20060101
C09D151/00; H05K 1/03 20060101 H05K001/03; B05D 3/02 20060101
B05D003/02 |
Claims
1. A method for manufacturing an organic-inorganic hybrid material
film of polymaleic anhydride-polyimide-silica comprising steps of:
(a) dissolving and reacting a dianhydride with a diamine in a
solvent to form polyamic acid; (b) reacting polymaleic anhydride
with the polyamic acid produced by the step (a) to form the
polymaleic anhydride grafting with --NH--CO-- group and oligomer
having carboxylic acid group at side chains; (c) adding a silane
coupling agent; (d) carrying out a chemical ring-closure of the
polyamic acid by adding a catalyst into a solution obtained from
step (c); (e) forming an organic-inorganic hybrid material solution
of polymaleic anhydride-polyimide-silica by adding an alkoxysilane
monomer having formula of Si(R3)4, where R3 may be the same or not
the same and represents halogens, C1-6 alkoxy group, C2-6 enyloxy
group and aryloxy group into a solution obtained from step (d); and
(f) forming an organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica by coating and curing the
organic-inorganic hybrid material solution of polymaleic
anhydride-polyimide-silica on a substrate.
2. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 1,
wherein the silane coupling agent of step (c) is an amine group
coupling agent having formula of H2N--R1-Si(R2)3, where R1
represents C1-6 alkylene group or arylene group; and R2 may be the
same or not the same and represents C1-6 alkoxy group, and polyamic
acid grafted with amine group coupling agents can be obtained by
reacting amine groups of H2N--R1-Si(R2)3 with anhydride groups of
polymaleic anhydride that is produced by step (b), in which the
moles of amine group coupling agents less than the diamine
thereof.
3. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 2,
wherein the amine group coupling agent having formula of
H2N--R1-Si(R2)3 is a coupling agent selected from the group
consisting of 3-amine-methyl trimethoxysilane (APrTMOS),
3-amine-propyl triethoxysilane (APrTEOS), 3-amine-phenyl
trimethoxysilane (APTMOS) and 3-amine-phenyl triethoxysilane
(APTEOS).
4. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 1,
wherein the silane coupling agent of step (c) is an isocyanic acid
group coupling agent having formula of OCN--R1-Si(R2)3, where R1
represents C1-6 alkylene group or arylene group; and R2 may be the
same or not the same and represents C1-6 alkoxy group, and polyamic
acid grafted with isocyanic acid group coupling agents at a
position of a side chain of the polymaleic anhydride can be
obtained by reacting isocyanic acid group groups of OCN--R1-Si(R2)3
with hydroxyl groups of diamine at a position of a side chain of
the polymaleic anhydride that is produced by step (b).
5. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 1,
wherein the alkoxysilane monomer having formula of Si(R3)4 used in
step (e) is a member selected from the group consisting of
tetramethoxy silane, tetraethoxy silane and tetrapropoxy
silane.
6. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 1,
further a coupling agent monomer having formula of R4Si(R5)3, where
R4 is a functional group with epoxy group at end and R5 may be the
same or not the same and represents halogens, C1-6 alkoxy group,
C2-6 enyloxy group and aryloxy group is added into a solution that
is produced by step (e) to carry out a hydrolytic condensation
reaction, and produce covalent bond combining to silica phase.
7. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 6,
wherein the coupling agent monomer having formula of R4Si(R5)3 is a
member selected from the group consisting of .gamma.-glycidoxy
propyl trimethoxy silane (GTMOS) and .gamma.-glycidoxy propyl
triethoxy silane (GTEOS).
8. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 1,
wherein the solvent used in step (a) is a member selected from the
group consisting of N-methyl pyrrolidin ketone,
N,N-dimethyl-formylamide, N,N-dimethyl-acetamide and diethylene
glycol monomethyl ether.
9. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 1,
wherein the catalyst used in step (d) is pyridine or
beta-picoline.
10. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 1,
wherein to the step (d), a dehydrating agent is added.
11. The method for manufacturing an organic-inorganic hybrid
material film of polymaleic anhydride-polyimide-silica of claim 10,
wherein the dehydrating agent is acetic anhydride, propionic
anhydride, butyric anhydride, valeric anhydride and their mixtures;
anhydrides of aromatic monocarboxylic acid; the mixture of
aliphatic anhydrides and aromatic anhydrides; carbodimides; and
aliphatic ketenes.
12. An organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica manufactured by the method of claim 1,
the polymaleic anhydride acting as a main chain, and the polymaleic
anhydride grafting with a plurality of short chains at side chain
positions, wherein each short chain has polyimide moiety and silica
moiety.
13. A prepreg formed of a fiberglass cloth cladding in the
organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica of claim 12.
14. A copper foil substrate including at least one copper foil
laminated with the prepreg of claim 13.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The invention relates to a method for manufacturing an
organic-inorganic hybrid material film, particularly to a method
for manufacturing an organic-inorganic hybrid material film of
polymaleic anhydride-polyimide-silica.
[0003] 2. Related Art
[0004] Composites can be manufactured by combining a variety of
materials such as polymers and inorganic compounds, and have
properties of both polymers and inorganic compounds. For example,
polymers are easy to process and inexpensive, and have excellent
properties such as high toughness, elasticity, corrosion
resistance, but have poor properties of heat resistance and
mechanical strength. On the other hand, inorganic compounds such as
ceramics are hard, and have low activity, excellent heat resistance
and mechanical strength, but are fragile and have a heavier weight.
A brand new material can be obtained by combining a variety of
materials with their advantages. Conventional composites have been
manufacturing by blending polymers such as polyethylene,
polypropylene, polystyrene and polymethyl methacrylate, nylon,
polyester and polyimide; and inorganic compounds such as calcium
carbonate, clay and silica. However, organic-inorganic hybrid
materials that are manufactured by chemical methods of sol-gel
route or self-assembly in combination to polymer moieties and
inorganic compound moieties may exhibit excellent properties that
are preferable than conventional composites thereof.
[0005] Polyimides are suitable in combination to inorganic
compounds to form organic-inorganic hybrid materials because
polyimides have excellent heat resistance, mechanical properties
and chemical resistance. Therefore, the organic-inorganic hybrid
materials containing polyimides are widely used in the aerospace
industry, electronic materials, etc. Now the polyimides that are
generally in use are mostly aromatic polyimides. However, most of
the aromatic polyimide cannot be dissolved in the solvent and is
non-thermoplastic, and thus difficult to process. Polyamic acid
that is precursor of polyimide can be dissolved in the solvent.
Therefore, polyimide may be formed by forming a desired shape by
the polyamic acid solution, and then imidization is carried
out.
[0006] However, imidization is accompanied by water evaporation
because the reaction temperature of thermal imidization has reached
more than 300.degree. C. that exceeds the boiling point of water.
Accordingly, the disadvantage of wrinkled surface of the thick film
formed of the polyimide resin by the thermal ring closure step will
occur. The temperature for film forming is hard to select properly.
On the other hand, the film formed of the polyamic acid fails to
keep a property of excellent temperature resistance of the
polyimide as the imidization is omitted. Also, polyamic acid
solution is hard to preserve, because hydrolysis of the polyamic
acid solution is easy to occur in presence of water.
[0007] Polyimides are used extensively in the electronic fields as
insulation film or protective coating on semiconductor devices.
Especially, aromatic polyimides play an important role for high
density and multi-function of flexible printed circuit substrates
and integrated circuits due to the excellent temperature
resistance, mechanic strength and insulation property.
[0008] Accordingly, precursor solution of polyimides is typically
used for the formation of interlayer insulation film or protective
coating of micro-circuit. The precursor solution of polyimides such
as polyamic acid (PAA) solution, polyamic acid acetate solution,
polyamic acid trimethylsilyl acetate solution and polyamic acid
bis(diethyl amide) solution may be formed by reacting diamine
compounds with tetracarboxylic dianhydride. The precursor solutions
of polyimides are all polymer solution with high degree of
polymerization. Typically, the film of polyimides is formed by
coating the polymer solution on a substrate such as copper or
glass, and then heated to carry out imidization and remove the
solvent.
[0009] However, it is required to reduce the concentration of
solute for obtaining a proper viscosity of the polymer solution
when coating the polymer solution with high degree of
polymerization. On the other hand, in order to increase the
production, it is required to increase the concentration of solute,
and thus the polymer solution has an increased viscosity and is
difficult for coating. Further, if polymers with low molecular
weight are manufactured to obtain a proper viscosity of the polymer
solution for coating, it is not able to form a film with excellent
temperature resistance and mechanic strength. Moreover, the polymer
solution is hard to preserve in a condition of maintaining the
original degree of polymerization for a long time.
SUMMARY OF THE INVENTION
[0010] An object of the invention is to provide, an
organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica in which a polymaleic
anhydride-polyimide phase contains polymaleic anhydride as a main
chain, and the polymaleic anhydride grafting with reactively
terminated functional groups for crosslinking at side chain
positions, wherein the short chain has polyimide structure. The
side chains are short that can decrease the degree of
polymerization, and thus can avoid polymer solution too much
viscous to form film by coating.
[0011] Another object of the invention is to provide a method for
manufacturing an organic-inorganic hybrid material film of
polymaleic anhydride-polyimide-silica in which a polymaleic
anhydride-polyimide phase contains polymaleic anhydride as a main
chain. Because the invention uses a chemical ring closure step, the
disadvantage of wrinkled surface of the thick film formed of the
polyimide resin by the thermal ring closure step can be
avoided.
[0012] Further another object of the invention is to provide a
prepreg which has excellent temperature resistance and mechanical
strength, and can be an insulation layer material for use in copper
foil substrates and circuit boards. Still another object of the
invention is to provide a copper foil substrate which has excellent
temperature resistance and mechanical strength, and bonds with
electronic elements to form an electronic device that can be
operated in a strict environment of high temperature and high
humidity without deterioration.
[0013] To accomplish the above object, there is provided an
organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica in which a polymaleic
anhydride-polyimide phase contains polymaleic anhydride as a main
chain, and the polymaleic anhydride grafting with reactively
terminated functional groups for crosslinking at side chain
positions, wherein the position of short chain has polyimide moiety
and silica moiety combining each other.
[0014] The invention provides a method for manufacturing an
organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica. The method comprises steps of: (i)
dissolving and reacting a dianhydride with a diamine in a solvent
to form polyamic acid; (ii) reacting polymaleic anhydride with the
polyamic acid produced by the step (i) under a temperature below
80.degree. C. to form the polymaleic anhydride grafting with
--NH--CO-- group and oligomer having carboxylic acid group at side
chains; (iii) adding a silane coupling agent; (iv) carrying out a
chemical ring-closure of the polyamic acid by adding a catalyst
into a solution obtained from step (iii); (v) forming an
organic-inorganic hybrid material solution of polymaleic
anhydride-polyimide-silica by adding an alkoxysilane monomer having
formula of Si(R3)4, where R3 may be the same or not the same and
represents halogens, C1-6 alkoxy group, C2-6 enyloxy group and
aryloxy group into a solution obtained from step (iv); and (vi)
forming an organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica by coating and curing the
organic-inorganic hybrid material solution of polymaleic
anhydride-polyimide-silica on a substrate.
[0015] Also, the invention provides a prepreg formed of a
fiberglass cloth impregnated in the above organic-inorganic hybrid
material solution of polymaleic anhydride-polyimide-silica.
Further, the invention provides a copper foil substrate including a
copper foil laminated with the above prepreg.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a flow chart of a method for manufacturing an
organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica of an embodiment of the present
invention.
[0017] FIG. 2 is a diagram showing reactions for manufacturing an
organic-inorganic hybrid material of polymaleic
anhydride-polyimide-silica of an embodiment of the present
invention, wherein a silane coupling agent for use in the reaction
is an amine group coupling agent having formula of
H2N--R1-Si(R2)3.
[0018] FIG. 3 is a diagram showing reactions for manufacturing an
organic-inorganic hybrid material of polymaleic
anhydride-polyimide-silica of another embodiment of the present
invention, wherein a silane coupling agent for use in the reaction
is an isocyanic acid group coupling agent having formula of
OCN--R1-Si(R2)3.
[0019] FIG. 4 is a graph showing IR absorption spectroscopy of an
organic-inorganic hybrid material of polymaleic
anhydride-polyimide-silica of an embodiment of the invention.
[0020] FIG. 5 is an analytical result of FIG. 4.
[0021] FIG. 6 is a graph showing phase transition of an
organic-inorganic hybrid material of polymaleic
anhydride-polyimide-silica of the invention measured by
differential scanning calorimetry (DSC).
[0022] FIG. 7 is a graph showing the weight residue of an
organic-inorganic hybrid material of polymaleic
anhydride-polyimide-silica of the invention when heated to various
temperatures.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Please refer to FIG. 1. FIG. 1 is a flow chart of a method
for manufacturing an organic-inorganic hybrid material film of
polymaleic anhydride-polyimide-silica of an embodiment of the
present invention. The method comprises steps of: dissolving and
reacting a dianhydride with a diamine in a solvent to form polyamic
acid, as shown in step S10; reacting polymaleic anhydride with the
polyamic acid produced by the step S10 under a temperature below
80.degree. C. to form the polymaleic anhydride grafting with
--NH--CO-- group and oligomer having carboxylic acid group at side
chains, as shown in step S12; adding a silane coupling agent, as
shown in step S14; carrying out a chemical ring-closure of the
polyamic acid by adding a catalyst into a solution obtained from
step S14, as shown in step S16; forming an organic-inorganic hybrid
material solution of polymaleic anhydride-polyimide-silica by
adding an alkoxysilane monomer having formula of Si(R3)4, where R3
may be the same or not the same and represents halogens, C1-6
alkoxy group, C2-6 enyloxy group and aryloxy group into a solution
obtained from step S16, as shown in step S18; and forming an
organic-inorganic hybrid material film of polymaleic
anhydride-polyimide-silica by coating and curing the
organic-inorganic hybrid material solution of polymaleic
anhydride-polyimide-silica on a substrate, as shown in step
S20.
[0024] Dianhydrides suitable for use in step S10 of the methods of
the invention include, but are not limited to: maleic anhydride,
substituted maleic anhydride, tetrahydrophthalic anhydride,
substituted tetrahydrophthalic anhydride, endomethylene
tetrahydrophthalic anhydride, substituted endomethylene
tetrahydrophthalic anhydride; aromatic dianhydrides, for example,
pyromellitic dianhydride (PMDA), 4,4'-biphthalic dianhydride
(BPDA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA),
1-(trifluoromethyl)-2,3,5,6-phenyltetracarboxylic dianhydride
(P3FDA), 1,4-bis(trifluoromethyl)-2,3,5,6-phenyltetracarboxylic
dianhydride (P6GDA),
1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-5,6-dicarboxylic
dianhydride,
1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-dicarboxylic
dianhydride,
1-(3',4'-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic
dianhydride,
1-(3',4'-dicarboxyphenyl)-3-methylindane-6,7-dicarboxylic
dianhydride, 2,3,9,10-perylene-tetracarboxylic dianhydride,
1,4,5,8-naphthalene-tetracarboxylic dianhydride,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
2,7-dicholronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
2,3,6,7-tetrachloronaphthalene-2,4,5,8-tetracarboxylic dianhydride,
phenanthryl-1,8,9,10-tetracarboxylic dianhydride,
3,3',4,4'-diphenylketone-tetracarboxylic dianhydride,
1,2',3,3'-diphenylketone-tetracarboxylic dianhydride,
3,3',4,4'-biphenyl-tetracarboxylic dianhydride,
3,3',4,4'-diphenylketone-tetracarboxylic dianhydride,
2,2',3,3'-biphenyl-tetracarboxylic dianhydride,
4,4'-(isopropylidene)diphthalic anhydride,
3,3'-(isopropylidene)diphthalic anhydride, 4,4'-oxy-diphthalic
anhydride, 4,4'-sulfanyl-diphthalic anhydride, 3,3'-oxy-diphthalic
anhydride, 4,4'-(methylene)diphthalic anhydride,
4,4'-(sulfur)diphthalic anhydride, 4,4'-(ethylene)diphthalic
anhydride, 2,3,6,7-naphthalene-tetracarboxylic dianhydride,
1,2,4,5-naphthalene-tetracarboxylic dianhydride,
1,2,5,6-naphthalene-tetracarboxylic dianhydride,
phenyl-1,2,3,4-tetracarboxylic dianhydride,
pyrazine-2,3,5,6-tetracarboxylic dianhydride, in which anhydrides
preferable for use include pyromellitic dianhydride,
4,4'-biphthalic dianhydride,
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA),
1-(trifluoromethyl)-2,3,5,6-phenyltetracarboxylic dianhydride
(P3FDA) and 1,4-bis(trifluoromethyl)-2,3,5,6-phenyltetracarboxylic
dianhydride (P6GDA).
[0025] Diamines suitable for use in step S10 of the methods of the
invention include, but are not limited to: 4,4'-oxydianiline (ODA),
5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane,
6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane,
4,4'-methylene-bis(o-chloroaniline), 3,3'-dichlorodianiline,
3,3'-sulfanyldianiline, 4,4'-diaminobenzophenone,
1,5-diaminonaphthalene, bis(4-aminophenyl) diethyl silane,
bis(4-aminophenyl)diphenyl silane,
bis(4-aminophenyl)ethyl-phosphine oxide,
N-(bis(4-aminophenyl))-N-methylamine,
N-(bis(4-aminophenyl))-N-phenylamine,
4,4'-methylene-bis(2-methylaniline),
4,4'-methylene-bis(2-methoxylaniline),
5,5'-methylene-bis(2-amino-phenol),
4,4'-methylene-bis(2-methylaniline),
4,4'-oxy-bis(2-methoxylaniline), 4,4'-oxy-bis(2-chloroaniline),
2,2'-bis(4-amino-phenol), 5,5'-oxy-bis(2-amino-phenol),
4,4'-sulfur-bis(2-methylaniline),
4,4'-sulfur-bis(2-methoxylaniline),
4,4'-sulfur-bis(2-chloroaniline),
4,4'-sulfanyl-bis(2-methylalanine),
4,4'-sulfanyl-bis(2-ethoxylalinine),
4,4'-sulfanyl-bis(2-chloroalinine),
5,5'-sulfanyl-bis(2-amino-phenol),
3,3'-dimethyl-4,4'-diaminobenzophenone,
3,3'-dimethoxyl-4,4'-diaminobenzophenone,
3,3'-dichloro-4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl,
m-phenylenediamine, p-phenylenediamine, 4,4'-methylene-dialanine,
4,4'-sulfur-dialanine, 4,4'-sulfanyl-dialanine,
4,4'-isopropylene-dialinine, 3,3'-dimethyldialinine,
3,3'-dimethoxyldialinine, 3,3'-dicarboxydialinine,
2,4-methylphenyldiamine, 2,5-methylphenyldiamine,
2,6-methylphenyldiamine, m-dimethylphenyldiamine,
2,4-diamino-5-chlorotoluene, 2,4-diamine-6-chlorotoluene, etc., in
which 4,4'-oxydianiline (ODA) is preferable.
[0026] The solvents preferable used in step S10 independently are,
for example, N-methyl pyrrolidin ketone, N,N-dimethyl-formylamide,
N,N-dimethyl-acetamide and diethylene glycol monomethyl ether. The
solvents preferable used in step S10 in mixture of two kinds are,
for example, N-methyl pyrrolidin ketone and diethylene glycol
monomethyl ether, N-methyl pyrrolidin ketone and methanol, N-methyl
pyrrolidin ketone and 2-methoxyethanol.
[0027] A polymaleic anhydride used in step S12 is a polymer with
maleic anhydride groups at position of a main chain. The silane
coupling agent used in step S14 may be an amine group coupling
agent having formula of H2N--R1-Si(R2)3, where R1 represents C1-6
alkylene group such as methylene, ethylene, propylene, butylene,
pentylidene and hexamethylene or arylene group such as phenylene
and naphthylene; and R2 may be the same or not the same and
represents C1-6 alkoxy group. Polyamic acid grafted with amine
group coupling agents can be obtained by reacting amine groups of
H2N--R1-Si(R2)3 with anhydride groups of polymaleic anhydride that
is produced by step S 12, in which the moles of amine group
coupling agents less than the diamine thereof. The amine group
coupling agent having formula of H2N--R1-Si(R2)3 is a coupling
agent selected from the group consisting of 3-amine-methyl
trimethoxysilane (APrTMOS), 3-amine-propyl triethoxysilane
(APrTEOS), 3-amine-phenyl trimethoxysilane (APTMOS) and
3-amine-phenyl triethoxysilane (APTEOS). Alternatively, the silane
coupling agent for use in step S14 may be an isocyanic acid group
coupling agent having formula of OCN--R1-Si(R2)3, where R1
represents C1-6 alkylene group such as methylene, ethylene,
propylene, butylene, pentylidene and hexamethylene or arylene group
such as phenylene and naphthylene; and R2 may be the same or not
the same and represents C1-6 alkoxy group. Polyamic acid grafted
with isocyanic acid group coupling agents at a position of a side
chain of the polymaleic anhydride can be obtained by reacting
isocyanic acid group groups of OCN--R1-Si(R2)3 with hydroxyl groups
of diamine at a position of a side chain of the polymaleic
anhydride that is produced by step S12.
[0028] Catalysts suitable used in step S16 may be pyridine or
beta-picoline. Other tertiary amine catalysts that have a similar
activity to pyridine and beta-picoline can also be used in the
method. These tertiary amines include alpha picoline, 3,4-lutidine,
3,5-lutidine, 4-picoline, 4-isopropylpyridine, N,N-dimethylbenzyl
amine, isoquinoline, 4-benzylpyridine, N,N-dimethyldodecylamine,
triethyl amine and the like. In addition, dehydrating agents may be
added in step S16. The suitable dehydrating agents include: (i)
aliphatic anhydrides such as acetic anhydride, propionic anhydride,
butyric anhydride, valeric anhydride and their mixtures; (ii)
anhydrides of aromatic monocarboxylic acid; (iii) the mixture of
aliphatic anhydrides and aromatic anhydrides; (iv) carbodimides;
and (v) aliphatic ketenes. Typically, the acetic anhydride is used
in excess of moles to amide acid functional groups of the polyamic
acid and the acetic anhydride is used in the range of 1.2-2.4 moles
based on per equivalent of polyamic acid. In one embodiment, the
tertiary amine catalyst is used in the same amount of moles of the
acetic anhydride.
[0029] The alkoxysilane monomer having formula of Si(R3)4 used in
step S18 may be selected from the group consisting of tetramethoxy
silane, tetraethoxy silane and tetrapropoxy silane. In addition, a
coupling agent monomer having formula of R4Si(R5)3, where R4 is a
functional group with epoxy group at end and R5 may be the same or
not the same and represents halogens, C1-6 alkoxy group, C2-6
enyloxy group and aryloxy group can be added into a solution that
is produced by step S18 to carry out a hydrolytic condensation
reaction, and produce covalent bond combining to silica phase. The
coupling agent monomer having formula of R4Si(R5)3 may be selected
from the group consisting of .gamma.-glycidoxy propyl trimethoxy
silane (GTMOS) and .gamma.-glycidoxy propyl triethoxy silane
(GTEOS).
[0030] Next, please refer to FIG. 2. FIG. 2 is a diagram showing
reactions for manufacturing an organic-inorganic hybrid material of
polymaleic anhydride-polyimide-silica of an embodiment of the
present invention, wherein a silane coupling agent for use in the
reaction is an amine group coupling agent having formula of
H2N--R1-Si(R2)3. In an embodiment, at first aromatic diamine (shown
as structural formula (1), where X is members selected from the
group consisting of C, O and benzene ring; and Y is H or CF3)
reacts with maleic anhydride monomers (shown as structural formula
(2)) to form polyamic acid (shown as structural formulas (3) and
(4)). Next, polymaleic anhydride is added to react with the
polyamic acid (shown as structural formulas (3)) produced by the
previous step under a temperature below 80.degree. C. to form the
polymaleic anhydride grafting with --NH--CO-- group and oligomer
having carboxylic acid group at side chains, followed by the
addition of an amine group coupling agent having formula of
H2N--R1-Si(R2)3, where R1 represents C1-6 alkylene group such as
methylene, ethylene, propylene, butylene, pentylidene and
hexamethylene or arylene group such as phenylene and naphthylene;
and R2 may be the same or not the same and represents C1-6 alkoxy
group to obtain polyamic acid grafted with amine group coupling
agents (shown as structural formula (5)) by reacting amine groups
of H2N--R1-Si(R2)3 with anhydride groups of polymaleic anhydride.
Also, polyamic acid shown as structural formula (6) is
obtained.
[0031] Next, a chemical ring-closure of the polyamic acid grafting
with --NH--CO-- group and oligomer having carboxylic acid group at
side chains is carried out by adding a catalyst to form a polyimide
grafting with an amine group coupling agent (shown as structural
formula (7)) and a polyimide shown as structural formula (8) is
obtained. Next, tetraethoxy silane (TEOS) was added in presence of
water and acidic catalyst or basic catalyst under a temperature
range of 15.degree. C. to 100.degree. C. to form an
organic-inorganic hybrid material solution of polymaleic
anhydride-polyimide-silica (shown as structural formula (9)) with
combining polyimide moiety and silica via covalent bond by a
hydrolytic condensation reaction of Si--OHof TEOS and the amine
group coupling agent. Also, a polyimide shown as structural formula
(10) is obtained. When the polyamic acid ring closes to form a
polyimide, the thermal crosslinking functional groups at the side
chain positions may also close. Therefore, the thermal ring-closure
step by directly heating to about 300.degree. C. is not suitable.
In the embodiment, a chemical ring-closure step is employed by
using catalyst and dehydrating agent reacting with the polyamic
acid at 100.degree. C. for 4 hours to form a polyimide grafting
with an amine group coupling agent (shown as structural formula
(7)) and a polyimide shown as structural formula (8).
[0032] Next, please refer to FIG. 3. FIG. 3 is a diagram showing
reactions for manufacturing an organic-inorganic hybrid material of
polymaleic anhydride-polyimide-silica of another embodiment of the
present invention, wherein a silane coupling agent for use in the
reaction is an isocyanic acid group coupling agent having formula
of OCN--R1-Si(R2)3. In an embodiment, at first aromatic diamine
(shown as structural formula (11), where X is members selected from
the group consisting of C, O and benzene ring; and Y is H or CF3)
reacts with maleic anhydride monomers (shown as structural formula
(12)) to form polyamic acid (shown as structural formulas (13) and
(14)). Next, polymaleic anhydride is added to react with the
polyamic acid (shown as structural formulas (13)) produced by the
previous step under a temperature below 80.degree. C. to form the
polymaleic anhydride grafting with --NH--CO-- group and oligomer
having carboxylic acid group at side chains, followed by the
addition of an amine group coupling agent having formula of
OCN--R1-Si(R2)3, where R1 represents C1-6 alkylene group such as
methylene, ethylene, propylene, butylene, pentylidene and
hexamethylene or arylene group such as phenylene and naphthylene;
and R2 may be the same or not the same and represents C1-6 alkoxy
group to obtain polyamic acid grafted with isocyanic acid group
coupling agents (shown as structural formula (15)) by reacting
isocyanic acid groups of OCN--R1-Si(R2)3 with hydroxyl groups of
aromatic diamine at side chains of polymaleic anhydride. Also,
polyamic acid shown as structural formula (16) is obtained.
[0033] Next, a chemical ring-closure of the polyamic acid grafting
with --NH--CO-- group and oligomer having carboxylic acid group at
side chains is carried out by adding a catalyst to form a polyimide
grafting with an isocyanic acid group coupling agent (shown as
structural formula (17)) and a polyimide shown as structural
formula (18) is obtained. Next, tetraethoxy silane (TEOS) was added
in presence of water and acidic catalyst or basic catalyst under a
temperature range of 15.degree. C. to 100.degree. C. to form an
organic-inorganic hybrid material solution of polymaleic
anhydride-polyimide-silica (shown as structural formula (19)) with
combining polyimide moiety and silica via covalent bond by a
hydrolytic condensation reaction of Si--OH of TEOS and the
isocyanic acid group coupling agent. Also, a polyimide shown as
structural formula (20) is obtained. When the polyamic acid ring
closes to form a polyimide, the thermal crosslinking functional
groups at the side chain positions may also close. Therefore, the
thermal ring-closure step by directly heating to about 300.degree.
C. is not suitable. In the embodiment, a chemical ring-closure step
is employed by using catalyst and dehydrating agent reacting with
the polyamic acid at 100.degree. C. for 4 hours to form a polyimide
grafting with an isocyanic acid group coupling agent (shown as
structural formula (17)) and a polyimide shown as structural
formula (18).
Example
[0034] To a 1 L 3-neck flask equipped with a mechanical stirring
device, reflux condenser introducing nitrogen gas was added 1.602 g
(8 mmol) 4,4'-oxydianiline (ODA), which was dissolved by stirring
vigorously in 200 g solvent of dimethyl-acetamide for 10 minutes,
followed by the slow addition of 4.443 g (10 mmol)
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), while
maintaining the solution at room temperature for 24 hours to obtain
a polyamic acid solution. To the polyamic acid solution was added
20 mmol acetic anhydride and 20 mmol pyridine, and heated to
100.degree. C. for 4 hours to complete chemical ring-closure of the
maleamic acid. After the temperature of resultant solution was
reduced to room temperature, 886 mg (4 mmol) 3-(triethoxysilyl)
propyl isocyanate was added, and stirred to react at room
temperature for 4 hours resulting in combining with polyimide. This
was followed by the addition of 1.250 g of tetramethoxy silane
(TMOS) and stirred for 30 minutes, followed by the addition of 30
mg de-ionized water to react for 24 hours at room temperature
resulting in the desired organic-inorganic hybrid material solution
of polymaleic anhydride-polyimide-silica.
[0035] The characteristic tests of the product were carried out,
and the results were shown in FIGS. 4-7. FIG. 4 is a graph showing
IR absorption spectroscopy of an organic-inorganic hybrid material
of polymaleic anhydride-polyimide-silica of an embodiment of the
invention. FIG. 5 is an analytical result of FIG. 4. As can be seen
in FIG. 4, wave numbers 1538 cm-1 and 1650 cm-1 represent
respectively N--H bending peak and C.dbd.O stretching peak of
polyamic acid structure. The above two peaks may disappear and new
peaks may form after ring closure of the polyamic acid and
formation of polyimide. The new peaks include wave number 1380 cm-1
representing tertiary amine of polyimide structure, wave numbers
730 cm-1 and 1770 cm-1 representing C.dbd.O stretching peak of
polyimide structure, as shown in FIG. 5. FIG. 6 is a graph showing
phase transition of an organic-inorganic hybrid material of
polymaleic anhydride-polyimide-silica of the invention measured by
differential scanning calorimetry (DSC). As can be seen in FIG. 6,
glass transition temperature of the product is about 150.degree. C.
FIG. 7 is a graph showing the weight residue of an
organic-inorganic hybrid material of polymaleic
anhydride-polyimide-silica of the invention when heated to various
temperatures. As can be seen in FIG. 7, 5 wt % thermal gravimetric
temperature of the product is about 288.degree. C.
[0036] Further, the invention provides a prepreg formed of a
fiberglass cloth impregnated in the above organic-inorganic hybrid
material solution of polymaleic anhydride-polyimide-silica. The
prepreg has excellent temperature resistance and mechanical
strength, and can be an insulation layer material for use in copper
foil substrates and circuit boards.
[0037] Also, the invention provides a copper foil substrate
including a copper foil laminated with the above prepreg. The
copper foil substrate has excellent temperature resistance and
mechanical strength, and bonds with electronic elements to form an
electronic device that can be operated in a strict environment of
high temperature and high humidity without deterioration.
[0038] While the invention is described in by way of examples and
in terms of preferred embodiments, it is to be understood that the
invention is not limited thereto. On the contrary, the aim is to
cover all modifications, alternatives and equivalents falling
within the spirit and scope of the invention as defined by the
appended claims.
* * * * *